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Producción Científica, Tripodal ligands with main group bridghead units are well established in coordination chemistry and single-site organometallic catalysis. Although a large number of tris(2-pyridyl) main group ligands [E(2-py)3] (E = main group element, 2-py = 2-pyridyl) spanning across the whole p-block are now synthetically acessible, only limited work has been done on the coordination chemistry on the tris(2-pyridyl) group 15 ligands for the heavier elements (As, Sb). In the current study we investigate the coordination chemistry of the ligand family E(6-Me-2-py)3 (E = As, Sb) and of the As(V) ligand O[double bond, length as m-dash]As(6-Me-2-py)3. The air- and mositure-stability of all of these main group ligands makes them especially attractive in future catalytic applications., Ministerio de Ciencia, Innovación y Universidades (project PGC2018-096880- A-I00), Ministerio de Economía, Industria y Competitividad - Fondo Social Europeo (contract RYC-2015-19035), Engineering and Physical Sciences Research Council - Royal Dutch Shell co. Ltd. (grant EP/R511870/1)

Tripodal ligands with main group bridghead units are well established in coordination chemistry and single-site organometallic catalysis. Although a large number of tris(2-pyridyl) main group ligands [E(2-py)